CN114069045A - Silane additive composition, electrolyte containing same and lithium ion battery - Google Patents

Silane additive composition, electrolyte containing same and lithium ion battery Download PDF

Info

Publication number
CN114069045A
CN114069045A CN202010756752.6A CN202010756752A CN114069045A CN 114069045 A CN114069045 A CN 114069045A CN 202010756752 A CN202010756752 A CN 202010756752A CN 114069045 A CN114069045 A CN 114069045A
Authority
CN
China
Prior art keywords
electrolyte
lithium
silane
total mass
additive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202010756752.6A
Other languages
Chinese (zh)
Inventor
丁祥欢
严红
李中凯
徐冲
李南
马国强
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Zhonglan New Energy Materials Co ltd
Zhejiang Chemical Industry Research Institute Co Ltd
Sinochem Lantian Co Ltd
Original Assignee
Zhejiang Zhonglan New Energy Materials Co ltd
Zhejiang Chemical Industry Research Institute Co Ltd
Sinochem Lantian Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang Zhonglan New Energy Materials Co ltd, Zhejiang Chemical Industry Research Institute Co Ltd, Sinochem Lantian Co Ltd filed Critical Zhejiang Zhonglan New Energy Materials Co ltd
Priority to CN202010756752.6A priority Critical patent/CN114069045A/en
Priority to JP2023503096A priority patent/JP2023533380A/en
Priority to US18/015,540 priority patent/US20230261262A1/en
Priority to EP21842970.2A priority patent/EP4184646A4/en
Priority to PCT/CN2021/106328 priority patent/WO2022012601A1/en
Priority to KR1020237003526A priority patent/KR20230029973A/en
Publication of CN114069045A publication Critical patent/CN114069045A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses a silane additive composition containing carbon-carbon triple bonds, an electrolyte containing the composition and a lithium ion battery, wherein the composition comprises the following components in parts by weight: the silane additive is used for inhibiting the gas generation of the battery cell and accounts for 0.01-10.0 percent of the total mass of the electrolyte; the fluorine-containing lithium salt additive is used for improving the initial impedance of the battery cell and inhibiting the impedance from continuously increasing in the circulating process, and accounts for 0.1-10.0 percent of the total mass of the electrolyte. The composition has the advantages of simultaneously improving the high-temperature storage performance, the high-temperature cycle performance, the rate performance and the low-temperature performance of the battery.

Description

Silane additive composition, electrolyte containing same and lithium ion battery
Technical Field
The invention relates to lithium ion battery electrolyte, in particular to a composition of a silane additive containing carbon-carbon triple bonds and a fluorine-containing lithium salt additive, electrolyte containing the composition and a lithium ion battery.
Background
High energy density is a development trend of lithium batteries, and common promotion methods include increasing the working voltage or increasing the nickel content in the positive electrode material, but both methods pose new challenges to the cycle performance and safety performance of the battery cell. Therefore, high-temperature cycle performance and high-temperature storage stability of the battery are of great interest.
In order to improve the high-temperature storage performance of the lithium ion battery, additives for improving the high-temperature performance, such as Vinylene Carbonate (VC), Vinyl Ethylene Carbonate (VEC), 1, 3-Propane Sultone (PS), 1, 3-propylene Propyl Sulfonate (PST), tris (trimethylsilyl) borate (TMSB), are generally added to the electrolyte, so that an SEI film is formed on the negative electrode by VC, VEC, and the like, thereby inhibiting the side reaction between the electrolyte and the negative electrode and improving the stability of the electrode under high-temperature storage. PS, PST, TMSB, and the like, in addition to the negative electrode film formation, can form a CEI-type protective film on the surface of the high-nickel positive electrode material, and inhibit the elution of metal ions in the high-nickel positive electrode and the corresponding parasitic reaction, thereby playing a role in improving the high-temperature storage performance of the lithium battery of the high-nickel positive electrode material.
However, the additives have the defects that VEC or VC has larger volume expansion (gas generation) after the high-temperature storage of the battery in a high-voltage battery system and has poorer effect of inhibiting the impedance growth speed of a battery core; the sulfonate additives such as PS, PST and the like have obvious effect of inhibiting gas generation of the battery cell, but the initial impedance and the impedance growth rate are higher, so that the low-temperature performance, the rate capability and the like of the battery are not favorable, and more importantly, PS is a carcinogen, is listed in a Reach controlled substance list, and the use of PS is increasingly limited. Homologs or structural analogs such as PST or 1, 4-Butane Sultone (BS) also present similar concerns and are not recommended. Although TMSB can improve the high-temperature performance of the high-nickel material system, the effect of suppressing gas generation of the battery cell is insufficient, and the effect of suppressing impedance increase is not good.
In summary, the existing high-temperature performance improving additive needs to improve the high-temperature storage performance, most interface protective films have high impedance and high impedance growth rate, and the rate capability, the low-temperature performance and the long-term cycling stability of the battery are deteriorated. Therefore, it is a current technical difficulty to improve the high-temperature storage performance and simultaneously consider the high-temperature cycle stability, the low-temperature performance and the rate performance of the battery.
Disclosure of Invention
In order to solve the technical problems, the invention provides a silane additive composition which simultaneously improves the high-temperature storage performance and the high-temperature cycle performance of a battery.
The purpose of the invention is realized by the following technical scheme:
use of a silane-based additive composition in an electrolyte, the composition comprising:
the silane additive is used for inhibiting the gas generation of the battery cell, accounts for 0.01-10.0% of the total mass of the electrolyte, and has the structure shown as the following formula (I):
Figure BDA0002611817220000021
wherein, R1, R2, R3 and R4 are independently selected from any one of alkyl, alkynyl, fluoroalkyl and fluoroalkynyl, and at least one of R1, R2, R3 and R4 contains a carbon-carbon triple bond;
the fluorine-containing lithium salt additive is used for improving the initial impedance of the battery cell and inhibiting the continuous increase of the impedance of the battery cell in the circulation process, and accounts for 0.1-10.0 percent of the total mass of the electrolyte.
More preferably, the silane additive accounts for 0.1-3.0% of the total mass of the electrolyte, and the fluorine-containing lithium salt additive accounts for 0.2-5.0% of the total mass of the electrolyte.
According to the application of the silane additive composition in the electrolyte, R1, R2, R3 and R4 are preferably independently selected from C1-C6 alkyl, C2-C6 alkynyl, fluoro-C1-C6 alkyl and fluoro-C2-C6 alkynyl, and more preferably, the silane additive is selected from at least one of the following structures:
Figure BDA0002611817220000031
the silane additive can be subjected to oxidative decomposition on the positive electrode in preference to the solvent, a stable protective film is formed on the surface of the positive electrode, parasitic reaction between the electrolyte and the positive electrode material is inhibited, and the dissolution of positive electrode metal ions is prevented, so that the high-temperature storage performance of the battery is improved. Meanwhile, compared with the existing high-temperature additive, the silane additive has lower initial impedance, and is beneficial to improving the comprehensive performance of the battery.
The fluorine-containing lithium salt additive is a fluorine-containing lithium salt compound having boron or phosphorus as a central ion, and is preferably at least one selected from lithium difluorooxalato borate (abbreviated as LiDFOB), lithium tetrafluoroborate (abbreviated as LiBF4)), lithium difluorobis (oxalato) phosphate (abbreviated as LiDFOP), and lithium tetrafluorooxalato phosphate (abbreviated as LiTFOP). The lithium salt additive containing fluorine can construct an interface film which has stronger ionic conductivity and is beneficial to charge migration, and the interface film can continuously modify a positive and negative electrode interface film, so that the continuous increase of the impedance of a battery cell in the battery circulation process is inhibited, and the long-term high-temperature circulation stability of the battery is improved.
By combining the silane additives and the fluoride salt additives in the electrolyte, the gas generation in the high-temperature storage process of the battery can be further inhibited, the initial impedance is reduced, the impedance increase in the battery circulation process is inhibited, the capacity recovery and capacity retention performance of the battery are improved, and the multiplying power and low-temperature discharge performance of the battery are improved.
The invention also provides a lithium ion battery electrolyte, which comprises lithium salt, an organic solvent and a composition of any one of the silane additives and the fluorine-containing lithium salt additive.
The lithium salt is selected from conventional lithium salts in electrolyte. Preferably, the lithium salt is at least one selected from lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide and lithium bis (trifluoromethylsulfonyl) imide, and the molar concentration of the lithium salt in the electrolyte is 0.4-1.6 mol/L. More preferably, the lithium salt comprises lithium hexafluorophosphate, and the molar concentration of the lithium hexafluorophosphate in the electrolyte is. 0.6 to 1.2 mol/L.
The organic solvent is selected from common solvents in electrolyte. Preferably, the organic solvent is at least one selected from the group consisting of a carbonate compound having 3-6 carbon atoms, a carboxylate compound having 3-8 carbon atoms, a sulfone compound and an ether compound. More preferably, the carbonate compound of C3-C6 is at least one selected from ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate and ethyl propyl carbonate; the carboxylic ester compound of C3-C8 is at least one selected from gamma-butyrolactone, methyl acetate, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, ethyl butyrate, propyl acetate and propyl propionate; the sulfone compound is selected from sulfolane; the ether compound is at least one of triglyme or tetraglyme. Most preferably, the carbonate compound of C3-C6 is at least one selected from ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate and ethyl propyl carbonate; the carboxylic ester compound of C3-C8 is at least one selected from gamma-butyrolactone, methyl acetate, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, ethyl butyrate, propyl acetate and propyl propionate; the sulfone compound is selected from sulfolane; the ether compound is at least one of triglyme or tetraglyme.
The invention also provides a lithium ion battery which comprises a positive electrode, a negative electrode, a diaphragm and the electrolyte.
The anode can be a common anode in the field of lithium batteries. Preferably, the positive active material is selected from nickel-cobalt-manganese ternary material LiNi1-x-y-zCoxMnyAlzO2Nickel, nickelOne of lithium manganate, lithium cobaltate, a lithium-rich manganese-based solid solution, lithium manganate or lithium iron phosphate, wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and x + y + z is more than or equal to 0 and less than or equal to 1.
The cathode is a cathode commonly used in the field of lithium batteries. Preferably, the negative electrode active material is selected from one of artificial graphite, coated natural graphite, a silicon-carbon negative electrode, a silicon negative electrode or lithium titanate.
The voltage of the lithium ion battery can be in a conventional battery voltage range of 2.0-4.2V or a high voltage test range of more than 4.2V.
The invention also provides a method for simultaneously improving the high-temperature storage performance and the high-temperature cycle performance of the battery, which comprises the following steps: a composition comprising any of the silane-based additives and a fluorine-containing lithium salt-based additive described above is added to an electrolyte solution.
Compared with the prior art, the invention has the beneficial effects that:
the silane additive containing carbon-carbon triple bonds can form a protective layer on the surface of the anode, so that parasitic reaction of electrolyte and an anode material in the high-temperature storage process is inhibited, catalytic decomposition of the anode material on the electrolyte is inhibited, and volume expansion in the high-temperature storage and high-temperature circulation processes is effectively improved; compared with the high-temperature additive in the prior art, the high-temperature additive has lower initial impedance and impedance growth rate. Moreover, the fluorine-containing lithium salt additive can simultaneously and continuously generate film forming reaction on the positive electrode and the negative electrode, adjust the structure and the components of the positive electrode and the negative electrode interfacial films, promote the positive electrode and the negative electrode to generate the interfacial films with low impedance and high stability, inhibit the continuous increase of the impedance in the circulation process, and improve the multiplying power, the low-temperature discharge and the long-term high-temperature circulation stability of the battery.
Therefore, the combination of the silane additive containing carbon-carbon triple bonds and the fluorine-containing lithium salt additive can simultaneously improve the high-temperature storage performance and the high-temperature cycle stability of the battery and give consideration to the low-temperature discharge performance and the rate capability of the battery when being applied to the ternary lithium ion battery or other high-voltage battery systems.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Preparation example:
preparing a basic electrolyte: mixing Ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC) in a high-purity argon glove box with oxygen content and water content both being not higher than 0.1ppm according to the mass ratio of EC: DEC: EMC ═ 3:2:5, and slowly adding lithium hexafluorophosphate (LiPF) into the mixed solution6) To a molar concentration of 1 mol/L.
Preparing a lithium ion battery: injecting the prepared lithium ion battery electrolyte into fully dried 4.3V LiNi0.83Co0.07Mn 0.2O2In the graphite battery, the battery is subjected to capacity grading test after standing at 45 ℃, formation and secondary sealing.
Example 1
The operation of this example is the same as that of the preparation except that: to the electrolyte, 0.5% by mass of compound 1 based on the total mass of the electrolyte and 0.5% by mass of lithium difluorooxalato borate (liddob) based on the total mass of the electrolyte were added.
Example 2
The operation of this example is the same as that of the preparation except that: to the electrolyte, 0.5% by mass of compound 1 based on the total mass of the electrolyte and 1.0% by mass of lithium difluorooxalato borate (liddob) based on the total mass of the electrolyte were added.
Example 3
The operation of this example is the same as that of the preparation except that: to the electrolyte, 0.5% by mass of compound 1 based on the total mass of the electrolyte and 2.0% by mass of lithium difluorooxalato borate (liddob) based on the total mass of the electrolyte were added.
Example 4
The operation of this example is the same as that of the preparation except that: to the electrolyte solution were added 0.5% by mass of compound 1 based on the total mass of the electrolyte solution and 3.0% by mass of lithium difluorooxalato borate (liddob) based on the total mass of the electrolyte solution.
Example 5
The operation of this example is the same as that of the preparation except that: to the electrolyte, 0.5% by mass of compound 1 based on the total mass of the electrolyte and 5.0% by mass of lithium difluorooxalato borate (liddob) based on the total mass of the electrolyte were added.
Example 6
The operation of this example is the same as that of the preparation except that: to the electrolyte solution were added 1.0% by mass of compound 1 based on the total mass of the electrolyte solution and 1.0% by mass of lithium difluorooxalato borate (liddob) based on the total mass of the electrolyte solution.
Example 7
The operation of this example is the same as that of the preparation except that: to the electrolyte solution were added 2.0% by mass of compound 1 based on the total mass of the electrolyte solution and 1.0% by mass of lithium difluorooxalato borate (liddob) based on the total mass of the electrolyte solution.
Example 8
The operation of this example is the same as that of the preparation except that: to the electrolyte solution were added 3.0% by mass of compound 1 based on the total mass of the electrolyte solution and 1.0% by mass of lithium difluorooxalato borate (liddob) based on the total mass of the electrolyte solution.
Example 9
The operation of this example is the same as that of the preparation except that: to the electrolyte solution were added 0.5% by mass of compound 3 based on the total mass of the electrolyte solution and 1.0% by mass of lithium difluorooxalato borate (liddob) based on the total mass of the electrolyte solution.
Example 10
The operation of this example is the same as that of the preparation except that: to the electrolyte, 0.5% by mass of compound 3 based on the total mass of the electrolyte and 1.0% by mass of lithium difluorophosphate bis (liddrop) based on the total mass of the electrolyte were added.
Example 11
The operation of this example is the same as that of the preparation except that: to the electrolyte, 0.5% by mass of the compound 3 based on the total mass of the electrolyte and 1.0% by mass of lithium tetrafluoro oxalate phosphate (litfoop) based on the total mass of the electrolyte were added.
Example 12
The operation of this example is the same as that of the preparation except that: to the electrolyte, 0.5% by mass of compound 3 based on the total mass of the electrolyte and 1.0% by mass of lithium tetrafluoroborate (LiBF4) based on the total mass of the electrolyte were added.
Example 13
The operation of this example is the same as that of the preparation except that: to the electrolyte, 0.5% by mass of compound 5 based on the total mass of the electrolyte and 1.0% by mass of lithium difluorooxalato borate (liddob) based on the total mass of the electrolyte were added.
Example 14
The operation of this example is the same as that of the preparation except that: to the electrolyte solution were added 0.5% by mass of compound 7 based on the total mass of the electrolyte solution and 1.0% by mass of lithium difluorooxalato borate (liddob) based on the total mass of the electrolyte solution.
Example 15
The operation of this example is the same as that of the preparation except that: to the electrolyte solution were added 0.5% by mass of compound 10 based on the total mass of the electrolyte solution and 1.0% by mass of lithium difluorooxalato borate (liddob) based on the total mass of the electrolyte solution.
Comparative example 1:
the operation of this comparative example is the same as that of the preparation example, i.e. the base electrolyte is used, without additives.
Comparative example 2:
the operation of this comparative example is the same as the preparation except that: 0.5% of compound 1 by mass of the total electrolyte was added to the electrolyte.
Comparative example 3:
the operation of this comparative example is the same as the preparation except that: 1.0% of compound 1 by mass of the total electrolyte was added to the electrolyte.
Comparative example 4:
the operation of this comparative example is the same as the preparation except that: lithium difluoroborate (LiDFOB) was added to the electrolyte in an amount of 1.0% based on the total mass of the electrolyte.
Comparative example 5:
the operation of this comparative example is the same as the preparation except that: 1, 3-Propane Sultone (PS) accounting for 1.0 percent of the total mass of the electrolyte is added into the electrolyte.
Comparative example 6:
the operation of this comparative example is the same as the preparation except that: 1.0% of 1, 3-Propane Sultone (PS) and 1.0% of lithium difluoro oxalato borate (LiDFOB) were added to the electrolyte solution based on the total mass of the electrolyte solution.
Comparative example 7:
the operation of this comparative example is the same as the preparation except that: adding 1.0% of compound 3 by total mass of the electrolyte into the electrolyte;
comparative example 8:
the operation of this comparative example is the same as the preparation except that: lithium difluorophosphate bis (oxalato) was added to the electrolyte in an amount of 1.0% by mass based on the total mass of the electrolyte (liddrop).
Comparative example 9:
the operation of this comparative example is the same as the preparation except that: 0.5% of vinyl-1, 3-Propane Sultone (PST) based on the total mass of the electrolyte was added to the electrolyte.
Comparative example 10:
the operation of this comparative example is the same as the preparation except that: 0.5% of PST and 1.0% of lithium difluorophosphate bis (LiDFOP) were added to the electrolyte solution, based on the total mass of the electrolyte solution.
Comparative example 11:
the operation of this comparative example is the same as the preparation except that: 0.5% of PST and 1.0% of lithium difluoroborate (LiDFOB) were added to the electrolyte solution based on the total mass of the electrolyte solution.
Comparative example 12:
the operation of this comparative example is the same as the preparation except that: trimethylsilylboronic acid (TMSB) was added to the electrolyte in an amount of 1.0% based on the total mass of the electrolyte.
Comparative example 13:
the operation of this comparative example is the same as the preparation except that: 1.0% by mass of trimethylsilylboronic acid (TMSB) and 0.5% by mass of lithium difluorooxalato borate (LiDFOB) were added to the electrolyte.
Initial DCR, low-temperature discharge at-20 ℃, 3C rate discharge of the battery, high-temperature cycle performance and high-temperature storage performance tests are respectively carried out on the nickel-cobalt-manganese ternary batteries in the embodiments 1 to 15 and the comparative examples 1 to 13, and the test results are shown in Table 1.
TABLE 1 Battery Performance test Table
Figure BDA0002611817220000101
Figure BDA0002611817220000111
From the results, the silane additive and the fluorine-containing lithium salt additive have synergistic effect, and the silane additive and the fluorine-containing lithium salt additive have one defect, so that the low-temperature and rate performance of the battery are considered while the high-temperature storage and high-temperature cycling stability is ensured. The silane additive and the fluorine-containing lithium salt additive are combined, and the comprehensive performance is better than that of the combination of the additive without additive, the additive with single silane or the additive with single fluorine-containing lithium salt and the common high-temperature additive (such as PS, PST, TMSB and the like) and the additive with fluorine-containing lithium salt in the comparative example.

Claims (12)

1. The application of the silane additive composition in the electrolyte is characterized in that: the composition comprises:
the silane additive is used for inhibiting the gas generation of the battery cell, accounts for 0.01-10.0% of the total mass of the electrolyte, and has the structure shown as the following formula (I):
Figure FDA0002611817210000011
wherein, R1, R2, R3 and R4 are independently selected from any one of alkyl, alkynyl, fluoroalkyl and fluoroalkynyl, and at least one of R1, R2, R3 and R4 contains a carbon-carbon triple bond;
the fluorine-containing lithium salt additive is used for improving the initial impedance of the battery cell and inhibiting the impedance increase of the battery cell in the circulation process, and accounts for 0.1-10.0 percent of the total mass of the electrolyte.
2. The use of the silane-based additive composition of claim 1 in an electrolyte solution, wherein: r1, R2, R3 and R4 are independently selected from one of C1-C6 alkyl, C2-C6 alkynyl, fluoro-C1-C6 alkyl and fluoro-C2-C6 alkynyl.
3. The use of the silane-based additive composition of claim 2 in an electrolyte solution, wherein: r1, R2, R3, R4 are independently selected from one of methyl, ethyl, trifluoromethyl, trifluoroethyl, ethynyl or propynyl.
4. The use of a silane-based additive composition according to claim 3 in an electrolyte solution, wherein: the silane additive is selected from at least one of the following structures:
Figure FDA0002611817210000021
5. use of the silane-based additive composition according to any one of claims 1 to 4 in an electrolyte solution, wherein: the silane additive accounts for 0.1-3.0% of the total mass of the electrolyte, and the fluorine-containing lithium salt additive accounts for 0.2-5.0% of the total mass of the electrolyte.
6. Use of the silane-based additive composition according to any one of claims 1 to 4 in an electrolyte solution, wherein: the fluorine-containing lithium salt additive is a fluorine-containing lithium salt compound taking boron or phosphorus as central ions.
7. The use of the silane-based additive composition of claim 6 in an electrolyte solution, wherein: the fluorine-containing lithium salt additive is selected from at least one of lithium difluoro oxalato borate, lithium tetrafluoroborate, lithium bis (oxalato) difluorophosphate and lithium tetrafluorooxalato phosphate.
8. The lithium ion battery electrolyte comprises lithium salt and an organic solvent, and is characterized in that: the electrolyte solution further comprises the silane-based additive composition of any one of claims 1 to 7.
9. The lithium ion battery electrolyte of claim 8, wherein: the lithium salt is selected from at least one of lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide and lithium bis (trifluoromethylsulfonyl) imide, and the molar concentration of the lithium salt in the electrolyte is 0.4-1.6 mol/L.
10. The lithium ion battery electrolyte of claim 8, wherein: the organic solvent is at least one selected from C3-C6 carbonate compounds, C3-C8 carboxylic ester compounds, sulfone compounds and ether compounds.
11. A lithium ion battery, characterized by: the lithium ion battery includes:
a positive electrode sheet containing a positive electrode active material, a negative electrode sheet containing a negative electrode active material, a separator, and the electrolyte according to any one of claims 8 to 10.
12. A method for simultaneously improving the high-temperature storage performance and the high-temperature cycle performance of a battery is characterized in that: the silane-based additive composition according to any one of claims 1 to 7 is added to an electrolyte solution.
CN202010756752.6A 2020-07-15 2020-07-31 Silane additive composition, electrolyte containing same and lithium ion battery Pending CN114069045A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CN202010756752.6A CN114069045A (en) 2020-07-31 2020-07-31 Silane additive composition, electrolyte containing same and lithium ion battery
JP2023503096A JP2023533380A (en) 2020-07-15 2021-07-14 Silane-based additive, electrolytic solution containing the additive, and lithium-ion battery
US18/015,540 US20230261262A1 (en) 2020-07-15 2021-07-14 Silane Additive, Electrolyte and Lithium Ion Battery Containing Same
EP21842970.2A EP4184646A4 (en) 2020-07-15 2021-07-14 Silane additive, electrolyte and lithium ion battery containing same
PCT/CN2021/106328 WO2022012601A1 (en) 2020-07-15 2021-07-14 Silane additive, electrolyte and lithium ion battery containing same
KR1020237003526A KR20230029973A (en) 2020-07-15 2021-07-14 Silane-based additive, electrolyte and lithium ion battery containing the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010756752.6A CN114069045A (en) 2020-07-31 2020-07-31 Silane additive composition, electrolyte containing same and lithium ion battery

Publications (1)

Publication Number Publication Date
CN114069045A true CN114069045A (en) 2022-02-18

Family

ID=80227641

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010756752.6A Pending CN114069045A (en) 2020-07-15 2020-07-31 Silane additive composition, electrolyte containing same and lithium ion battery

Country Status (1)

Country Link
CN (1) CN114069045A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113948770A (en) * 2021-10-12 2022-01-18 远景动力技术(江苏)有限公司 Electrolyte for improving high-temperature storage characteristics of battery and lithium ion battery

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105206874A (en) * 2015-10-19 2015-12-30 东莞市凯欣电池材料有限公司 Alkynyl silane containing lithium-ion battery electrolyte and lithium-ion battery utilizing same
US20180191032A1 (en) * 2016-12-29 2018-07-05 Contemporary Amperex Technology Co., Limited Electrolyte and lithium-ion battery
WO2019111983A1 (en) * 2017-12-06 2019-06-13 セントラル硝子株式会社 Electrolyte solution for nonaqueous electrolyte batteries, and nonaqueous electrolyte battery using same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105206874A (en) * 2015-10-19 2015-12-30 东莞市凯欣电池材料有限公司 Alkynyl silane containing lithium-ion battery electrolyte and lithium-ion battery utilizing same
US20180191032A1 (en) * 2016-12-29 2018-07-05 Contemporary Amperex Technology Co., Limited Electrolyte and lithium-ion battery
WO2019111983A1 (en) * 2017-12-06 2019-06-13 セントラル硝子株式会社 Electrolyte solution for nonaqueous electrolyte batteries, and nonaqueous electrolyte battery using same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113948770A (en) * 2021-10-12 2022-01-18 远景动力技术(江苏)有限公司 Electrolyte for improving high-temperature storage characteristics of battery and lithium ion battery
CN113948770B (en) * 2021-10-12 2024-01-30 远景动力技术(江苏)有限公司 Electrolyte for improving high-temperature storage characteristics of battery and lithium ion battery

Similar Documents

Publication Publication Date Title
CN111430796B (en) Lithium ion battery electrolyte and lithium ion battery containing same
CN110931865A (en) Novel additive-containing electrolyte for lithium ion battery and lithium ion battery
CN111029655A (en) Lithium ion battery electrolyte and lithium ion battery containing same
CN112928332A (en) High-voltage lithium ion battery non-aqueous electrolyte and lithium ion battery
CN113078358A (en) Lithium ion battery non-aqueous electrolyte and lithium ion battery thereof
CN111146499B (en) Lithium ion battery electrolyte and lithium ion battery containing same
CN113991178A (en) Non-aqueous electrolyte of lithium ion battery and application thereof
CN110416611B (en) Non-aqueous electrolyte of lithium ion battery and lithium ion battery using same
CN111883834B (en) Non-aqueous lithium ion battery electrolyte additive, electrolyte containing non-aqueous lithium ion battery electrolyte additive and lithium ion battery
CN114069045A (en) Silane additive composition, electrolyte containing same and lithium ion battery
US20230261262A1 (en) Silane Additive, Electrolyte and Lithium Ion Battery Containing Same
CN115498265A (en) Electrolyte, preparation method thereof and lithium ion battery containing electrolyte
CN116936930A (en) Pseudo high-concentration electrolyte, preparation method thereof and application thereof in lithium ion battery
CN112186253B (en) Lithium ion battery non-aqueous electrolyte and lithium ion battery
CN114566711A (en) Electrolyte, preparation method thereof and high-nickel lithium ion battery containing electrolyte
CN110247116B (en) Non-aqueous electrolyte of lithium ion battery and lithium ion battery using same
CN113948768A (en) Silane additive, electrolyte containing same and lithium ion battery
CN109802177B (en) Electrolyte containing silicon solvent and pyridine additive and lithium ion battery using electrolyte
CN114695958A (en) Electrolyte for inhibiting side reaction of battery anode material and lithium ion battery
CN114824469A (en) Electrolyte containing high-voltage high-temperature additive composition and lithium ion battery
CN114695960A (en) Novel additive with high and low temperature performance, preparation method and application thereof
CN111952667A (en) Electrolyte additive, electrolyte containing additive and lithium ion battery
CN115732756B (en) Electrolyte and secondary battery using same
CN116487707B (en) Lithium ion battery and electrolyte thereof
CN115706261B (en) Nonaqueous electrolyte and lithium ion battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination